Search

Gas chromatography is typically operated in isothermal mode for optimum separation of a mixture of compounds with a narrow boiling point range, or in temperature-programmed mode, which strives to achieve a compromise between separation efficiency and time. Temperature gradients also keep the peak widths nearly constant over a wide range of retention times, enhancing the detectability of the later eluting peaks. In this chapter, the use of negative thermal gradients for gas chromatography (NTGGC) – for the sake of simplicity, subsequently only denoted as thermal gradient-gas chromatography, TGGC – shall be discussed. (N)TGGC is achieved by producing a stationary temperature gradient along the relatively short GC column in a proprietary experimental setup that allows cooling on one end of the column and heating on the other. The sample is injected into the hot end of the GC column, and analytes move towards the colder end of the column. Along their passage through the column, they are focused by the increasingly lower temperature of the stationary phase. This leads to a focusing of the peaks as they reach the cold column end. With appropriate temperature programming, very fast (sub-minute) chromatography with excellent resolution can be achieved on short GC columns. The present contribution will both discuss the theory behind this unusual, but highly performant mode of gas chromatographic separation, and also the hardware aspects of this technique. Relevant examples will be presented which highlight both the speed and the separation power by which (N)TGGC excels in comparison with regular temperature-programmed GC.

The composition of walnut oils is affected by multiple factors including their variety, their geographical location, and the environmental factors. In this study, the fatty acid composition of walnut oils from Greece and Bulgaria was assessed by gas chromatography coupled with flame ionization detection (GC-FID). The derivatization process involved the use of 14% BF3 after alkaline hydrolysis, and was optimized after investigating the effect of temperature (50–100℃) and methylation time (5–30 min). Twenty walnut oils originating from Greece and Bulgaria were analyzed, and the methyl esters of palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid were tentatively identified on the basis of their commercially available standards, and quantitatively determined. The method demonstrated good linearity (r2 > 0.999) and adequate recoveries (RE = 86.2–92.5%, n = 6). Precision was expressed as repeatability (intra-day precision, n = 3), and as reproducibility (inter-day precision (n = 9) and the results ranged between 2.7 and 4.6%RSD for intra-day experiments, and 4.1–5.8%RSD for inter-day experiments. The limits of detection (LODs) and limits of quantification (LOQs) ranged between 0.21–0.32 mg/kg and 0.63–0.97 mg/kg, respectively. The determined fatty acid methyl esters were quantified and the results were analyzed by Student’s t-test, principal component analysis (PCA), and hierarchical clustering to investigate the differences of the lipid fraction of the walnut oils according to their geographical origin.

Background:: Nuts have been incorporated into guidelines for healthy eating since they contain considerable amounts of antioxidants and their effects are related to health benefits since they contribute to the prevention of nutritional deficiencies. The micronutrient characterization is based mainly on the determination of phenolics, which is the most abundant class of bioactive compounds in nuts. Terpenes constitute another class of bioactive compounds that are present in nuts and show high volatility. The analysis of phenolic compounds and terpenes is a very demanding task that requires optimization of the chromatographic conditions to improve the separation of the components. Moreover, nuts are rich in unsaturated fatty acids and they are therefore considered as cardioprotective. Gas chromatography is the predominant instrumental analytical technique for the determination of derivatized fatty acids and terpenes in food matrices, while high performance liquid chromatography is currently the most popular technique for the determination of phenolic compounds. Objective:: This review summarizes all the recent advances in the optimization of the chromatographic conditions for the determination of phenolic compounds, fatty acids and terpenes in nuts. Conclusion:: The state-of-the art in the technology available is critically discussed, exploring new analytical approaches to reduce the time of analysis and improve the performance of the chromatographic systems in terms of precision, reproducibility, limits of detection and quantification and overall quality of the results.

A novel micro–meso porous activated carbon/Fe3O4 (Bm) composite was synthesized from the active charcoal precursor BAX-1500 and used in the magnetic solid-phase extraction (MSPE) of caffeine prior to its determination by gas chromatography-mass spectrometry (GC-MS). The main factors affecting the extraction and desorption steps of the MSPE procedure were investigated and optimized. These factors include extraction time, sorbent mass and salt addition for the adsorption step and type of eluent, desorption time and volume of desorption solution for the desorption step. Under optimum conditions, the absolute extraction recovery was found to be 91.1% and good linearity was observed in the investigated concentration range of 0.6–12.5 ng mL−1 (R2 = 0.9997). The limit of detection was 0.18 ng mL−1 and the limit of quantification was 0.60 ng mL−1. The method was successfully applied to the analysis of surface water samples. The proposed MSPE method is simple, rapid, sensitive and environmentally friendly.

We present a novel sample preparation method for the extraction and preconcentration of volatile organic compounds from whiskey samples prior to their determination by comprehensive two-dimensional gas chromatography (GC × GC) coupled to mass spectrometry (MS). Sample preparation of the volatile compounds, important for the organoleptic characteristics of different whiskeys and their acceptance and liking by the consumers, is based on the use of the solid-phase microextraction (SPME) Arrow. After optimization, the proposed method was compared with conventional SPME regarding the analysis of different types of whiskey (i.e., Irish whiskey, single malt Scotch whiskey and blended Scotch whiskey) and was shown to exhibit an up to a factor of six higher sensitivity and better repeatability by a factor of up to five, depending on the compound class. A total of 167 volatile organic compounds, including terpenes, alcohols, esters, carboxylic acids, ketones, were tentatively-identified using the SPME Arrow technique, while a significantly lower number of compounds (126) were determined by means of conventional SPME. SPME Arrow combined with GC × GC-MS was demonstrated to be a powerful analytical tool for the exploration of the volatile profile of complex samples, allowing to identify differences in important flavour compounds for the three different types of whiskey investigated.

Benzoyl urea insecticides are a class of pesticides used in agriculture for the inhibition of chitin synthesis in pests. These compounds are persistent in environmental samples, and thus their monitoring is necessary to avoid detrimental effects to human health and the environment. Magnet integrated fabric phase sorptive extraction (MI-FPSE) is a recently introduced sample preparation technique that combines sample stirring and analyte extraction into one stand-alone device. However, the applicability and the potential benefits of this technique in environmental analysis remain unexplored. In the present study, MI-FPSE was employed for the first time for the extraction and preconcentration of benzoyl urea insecticides (i.e., diflubenzuron, triflumuron, hexaflumuron, lufenuron and chlorfluazuron) from environmental water samples prior to their determination by high performance liquid chromatography-diode array detection (HPLC-DAD). The main factors affecting the performance of the proposed methodology were thoroughly investigated and optimized and the MI-FPSE-HPLC-DAD method was validated. The proposed method enabled the handling of relatively high sample quantity resulting in high preconcentration factors (501 and 731) and good sensitivity. Under optimum conditions, the limits of detection and the limits of quantification for the benzoyl urea insecticides were 0.06 ng mL

This study introduces the first mid-infrared (IR)–based method for determining the fatty acid composition of human milk. A representative milk lipid fraction was obtained by applying a rapid and solvent-free two-step centrifugation method. Attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy was applied to record absorbance spectra of pure milk fat. The obtained spectra were compared to whole human milk transmission spectra, revealing the significantly higher degree of fatty acid–related spectral features in ATR FT-IR spectra. Partial least squares (PLS)–based multivariate regression equations were established by relating ATR FT-IR spectra to fatty acid reference concentrations, obtained with gas chromatography–mass spectrometry (GC-MS). Good predictions were achieved for the most important fatty acid sum parameters: saturated fatty acids (SAT, R2CV = 0.94), monounsaturated fatty acids (MONO, R2CV = 0.85), polyunsaturated fatty acids (PUFA, R2CV = 0.87), unsaturated fatty acids (UNSAT, R2CV = 0.91), short-chain fatty acids (SCFA, R2CV = 0.79), medium-chain fatty acids (MCFA, R2CV = 0.97), and long-chain fatty acids (LCFA, R2CV = 0.88). The PLS selectivity ratio (SR) was calculated in order to optimize and verify each individual calibration model. All mid-IR regions with high SR could be assigned to absorbances from fatty acids, indicating high validity of the obtained models.

This study presents a fabric phase sorptive extraction (FPSE) protocol for the isolation and preconcentration of four selected polycyclic aromatic hydrocarbons from tea samples and herbal infusions, followed by their separation and quantification by gas chromatography-mass spectrometry (GC-MS). In FPSE, extraction of the target analytes is performed utilizing a flexible fabric substrate that is coated with a highly efficient sol-gel sorbent. In this work, eighteen different FPSE membranes were examined, with the highest extraction recoveries being observed with the sol-gel C

The response behavior and performance characteristics of the recently introduced barrier discharge ionization detector (BID) for gas chromatography (GC-BID) were investigated by analyzing d...

Organic contamination in freshwater samples has never been investigated at the western shore of Admiralty Bay. Therefore, the presence of polycyclic aromatic hydrocarbons (PAHs) in five different sites distributed along a shore running from the Arctowski Station to the Baranowski Glacier was studied. Moreover, organic compounds such as n-alkanes, toluene and ethylbenzene were also noted. Increased ΣPAHs in late Austral summer 2016 are the result of long-range atmospheric transport of air masses from South America, confirmed by 10-day backward air mass trajectories analysis. The presence of n-alkanes and other hydrocarbons, as well as the evaluation of PAH indices (e.g. ΣLMW/ΣHMW* > 1), shows the use of fuel and indicate local human activity. As a final conclusion, our analysis indicates a mixed origin of PAHs (global and local). The presence of PAHs and other hydrocarbons in the water environment may constitute a potentially negative effect on the Antarctic ecosystem and it should be investigated in detail during further research (//*ΣLMW—sum of low molecular weight PAHs (two- and three-ring PAHs); ΣHMW—sum of high molecular weight PAHs (four- and five-ring PAHs)//). Graphical abstract Electronic supplementary material The online version of this article (10.1007/s11356-019-05045-w) contains supplementary material, which is available to authorized users.

The determination of triazine herbicides in water samples is of utmost importance, due to their persistence and excessive use. However, since the concentration of triazine pesticides in real samples is low, an extraction/preconcentration step is typically required. Capsule phase microextraction (CPME) is a recently introduced sample preparation technique in which highly efficient sol-gel sorbents are encapsulated in a tubular polymer membrane. This particular design integrates the filtration and stirring mechanism into one extraction device, enabling the application of CPME for in situ sampling. In this study, CPME coupled to high performance liquid chromatography-diode array detection (HPLC-DAD) was employed for the first time for the determination of six triazine herbicides (i.e., simazine, cyanazine, atrazine, prometryn, terbuthylazine and propazine) in water samples. Microextraction capsules containing a moderately hydrophobic sol‐gel Carbowax 20 M sorbent provided the highest extraction efficiency towards the examined pesticides. The main parameters affecting the adsorption and desorption steps of the CPME procedure were investigated and optimized. Under the selected conditions, limits of detection (signal/noise = 3.3) were 0.15 ng mL−1 for the target analytes. Moreover, the relative standard deviation for the within-day and between-days repeatability were less than 7.2% and 9.9%, respectively. The method was successfully applied to the analysis of mineral water, tap water, rainwater and lake water samples. The reported protocol could overcome the need for sample filtration prior to the sample preparation of the water samples, resulting in simplification of the overall sample handling, improved data quality with minimal loss of analytes and reduced sample preparation cost.

In the present study, a novel approach for mid-infrared (IR)-based prediction of bovine milk fatty acid composition is introduced. A rapid, solvent-free, two-step centrifugation method was applied in order to obtain representative milk fat fractions. IR spectra of pure milk lipids were recorded with attenuated total reflection Fourier-transform infrared (ATR-FT-IR) spectroscopy. Comparison to the IR transmission spectra of whole milk revealed a higher amount of significant spectral information for fatty acid analysis. Partial least squares (PLS) regression models were calculated to relate the IR spectra to gas chromatography/mass spectrometry (GC/MS) reference values, providing particularly good predictions for fatty acid sum parameters as well as for the following individual fatty acids: C10:0 (R2P = 0.99), C12:0 (R2P = 0.97), C14:0 (R2P = 0.88), C16:0 (R2P = 0.81), C18:0 (R2P = 0.93), and C18:1cis (R2P = 0.95). The IR wavenumber ranges for the individual regression models were optimized and validated by calculation of the PLS selectivity ratio. Based on a set of 45 milk samples, the obtained PLS figures of merit are significantly better than those reported in literature using whole milk transmission spectra and larger datasets. In this context, direct IR measurement of the milk fat fraction inherently eliminates covariation structures between fatty acids and total fat content, which poses a common problem in IR-based milk fat profiling. The combination of solvent-free lipid separation and ATR-FT-IR spectroscopy represents a novel approach for fast fatty acid prediction, with the potential for high-throughput application in routine lab operation.

It is challenging to establish a correlation between the agronomical practices and the volatile profile of high-value agricultural products. In this study, the volatile metabolome of walnut oils from conventional and organic farming type was explored by HS-SPME-GC-MS. The SPME protocol was optimized after evaluating the effects of extraction time, extraction temperature, and sample mass. The optimum parameters involved the extraction of 0.500 g walnut oil at 40 °C within 60 min. Twenty Greek walnut oils produced with conventional and organic farming were analyzed and 41 volatile compounds were identified. The determined compounds were semi-quantified, and further processed with chemometrics. Agglomerative hierarchical clustering (AHC) and principal component analysis (PCA) were used. A robust classification model was developed using sparse partial least squares–discriminant analysis (sPLS-DA) for the discrimination of walnut oils into conventional and organic, establishing volatile markers that could be used to guarantee the type of farming.

A novel micro-meso porous activated carbon/Fe

A novel sample preparation method based on the use of the Arrow solid-phase microextraction device was used to extract and preconcentrate volatile organic compounds (VOCs) from milk samples prior to their determination by gas chromatography&ndash, mass spectrometry (GC-MS). The experimental parameters of the solid-phase microextraction (SPME) Arrow method were evaluated in terms of fiber type, sample volume, extraction temperature, extraction time, stirring rate and salt addition. Under the optimum extraction conditions, the SPME Arrow was compared with conventional SPME fibers to evaluate the effectiveness of the SPME Arrow method. Evaluation of the conventional SPME procedure was also performed under optimized conditions, for appropriate method comparison. Due to the larger sorption phase volume of SPME Arrow, a higher sensitivity and reproducibility were observed for the determined chromatographic peaks in comparison with conventional SPME fibers. The use of Carbon wide range (WR) SPME Arrow/polydimethylsiloxane (CAR/PDMS) SPME Arrow fibers leads to a compound-dependent improvement of a factor of 4&ndash, 5x over the classical SPME setup. Moreover, the relative standard deviation (RSD) of the total volatiles for a conventional SPME procedure was 12.5%, while for SPME Arrow it was 6.2%. Finally, the novel method was successfully employed for the analysis of commercially available milk samples. The findings of this study indicate that SPME Arrow can be effectively used for the determination of volatile organic compounds in complex food matrixes.

The main objective of the present work was to develop a method for the simultaneous and comprehensive analysis of (poly-)phenolic and flavonoid compounds with liquid chromatography with diode array and mass spectrometric detection and its application to green asparagus samples. To this end, a representative set of polyphenols was used to develop the method. A through method validation was carried out with these. The method was applied to asparagus samples known as a healthy vegetable being rich in bioactive compounds. Polyphenol contents of asparagus samples were determined by carrying out quantitative and qualitative analyses by LC-DAD-ESI/MS. In this context asparagus sample extracts were obtained using solvents of different polarity. The results were evaluated statistically and showed that rutin is the major phenolic compound in asparagus. This demonstrates the versatility of this rapid and sensitive method for the simultaneous analysis of (poly-)phenolic and flavonoid compounds which was successfully applied to asparagus samples.

Graphene oxide (GO) is a chemical compound with a form similar to graphene that consists of one-atom-thick two-dimensional layers of sp2-bonded carbon. Graphene oxide exhibits high hydrophilicity and dispersibility. Thus, it is difficult to be separated from aqueous solutions. Therefore, functionalization with magnetic nanoparticles is performed in order to prepare a magnetic GO nanocomposite that combines the sufficient adsorption capacity of graphene oxide and the convenience of magnetic separation. Moreover, the magnetic material can be further functionalized with different groups to prevent aggregation and extends its potential application. Until today, a plethora of magnetic GO hybrid materials have been synthesized and successfully employed for the magnetic solid-phase extraction of organic compounds from environmental, agricultural, biological, and food samples. The developed GO nanocomposites exhibit satisfactory stability in aqueous solutions, as well as sufficient surface area. Thus, they are considered as an alternative to conventional sorbents by enriching the analytical toolbox for the analysis of trace organic compounds.

The existence of interfacial carbides is a well-known phenomenon in Al/diamond composites, although quantitative analyses are not described so far. The control of the formation of interfacial carbides while processing Al(Si)/diamond composites is of vital interest as a degradation of thermophysical properties appears upon excessive formation. Analytical quantification was performed by GC–MS measurements of gaseous species released upon dissolving the matrix and interfacial reaction products in aqueous NaOH solutions and the CH4/N2 ratio of the evolving reaction gases can be used for quantification. Although the formation of interfacial carbides is significantly suppressed by adding Si to Al, also a decline in composite thermal conductivity is observed in particular with increasing contact time between the liquid metal and the diamond particles during gas pressure infiltration. Furthermore, surface termination of diamond particles positively affects composite thermal conductivity as oxygenated diamond surfaces will result in an increase in composite thermal conductivity compared to hydrogenated ones. In order to understand the mechanisms responsible for all impacts on the thermal conductivity and thermal conductance behaviour, the metal/diamond interface was electrochemical etched and characterized by SEM. Selected specimens were also cut by an ultrashort pulsed laser system to characterize interfacial layers at the virgin cross section in the reactive system Al/diamond.

Capsule phase microextraction (CPME) is a recently introduced environmentally friendly sample preparation technique that integrates both filtration and stirring mechanism into the extraction device. In this study, CPME was employed for the first time for the extraction of four polycyclic aromatic hydrocarbons (naphthalene, fluorene, phenanthrene and pyrene) from water samples prior to their determination by gas chromatography-mass spectrometry (GC–MS). The microextraction capsules were made of two porous polypropylene tubes that are welded to each other; one tube contained the magnetic rod, and the other tube contained the sorbent. Various sol–gel hybrid sorbents were evaluated. Microextraction capsules containing sol‐gel poly(caprolactone)-poly(dimethylsiloxane)-poly(caprolactone) (PCAP-PDMS-PCAP) sorbent provided the highest extraction efficiency. The main parameters (e.g., adsorption time, sample volume, stirring rate, addition of salt, type of eluent, desorption time and elution volume) affecting the steps of the CPME procedure were evaluated. Under the selected conditions, limits of detection (signal/noise = 3.3) ranged between 0.03 and 0.07 ng mL−1 for the selected PAHs. The relative standard deviation for the within-day and between-days repeatability were lower than 7.7% and 8.5%, respectively. Moreover, the CPME method exhibited good linearity and reusability of the microextraction capsules. The method was successfully applied to the analysis of tap water, mineral water and lake water samples. Relative recoveries ranged between 94.3 and 109.8%. The herein reported green method could efficiently simplify the overall sample preparation process, since it overcomes the requirements of sample filtration before the extraction and the solvent evaporation and sample reconstitution after the extraction.

A novel magnetic graphene oxide nanocomposite modified with polyaniline (Fe3O4@GO-PANI) was synthesized and applied for the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons (PAHs) (i.e. fluorene, phenanthrene and pyrene) and nitrated polycyclic aromatic hydrocarbons (N-PAHs) (i.e. 2-nitrofluorene, 9-nitroanthracene, 1-nitropyrene and 3-nitrofluoranthene) prior to their determination by gas chromatography-mass spectrometry. The prepared nanomaterial was characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform-infrared spectroscopy. The main experimental parameters affecting the extraction and desorption steps of the MSPE procedure were investigated and optimized. Under optimum conditions, coefficients of determination (r2) ranged between 0.9970 and 0.9995, limits of detection (LODs, S/N = 3) ranged between 0.04–0.05 ng mL−1 for PAHs and 0.01–0.11 ng mL−1 for N-PAHs, while the relative standard deviation for intra-day and inter-day repeatability were lower than 10.0% for PAHs and N-PAHs. The method was successfully applied to the analysis of tap, mineral and river water samples. Relative recoveries in spiked water samples ranged between from 91.6 to 114% and from 92.3 to 110% for PAHs and N-PAHs, respectively. The proposed method is simple, rapid, sensitive and the Fe3O4@GO-PANI sorbent can be reused for at least 15 times without significant decrease in extraction recovery.

Lithium Ion Batteries (LIB) find not only wide use in portable devices and consumer electronics, but also attract increasing attention in stationary energy storage and the automotive sector. In this regard, LIBs play a significant role as intermediate energy storage due to their high volumetric and gravimetric energy, high power density, and long cycle life. To achieve the required performance, the interaction of novel anode and cathode materials is of paramount interest. Particularly, the safety of cell operation must be assessed with respect to the formation of volatile and reactive species during cycling which can negatively alter cell components. Gas chromatography mass spectroscopy (GCMS) has proven to be a reliable tool for species detection. Unfortunately, conventional GC systems lack time resolution for in-situ gas analysis regarding fast processes, for example battery failure. Therefore, developing operando testing methods with improved time resolution is key to giving insight into electrolyte alterations during battery operation. Here one of them, a novel multiplex injection method is presented as a monitoring technique for gas species arising from the decomposition of conventional LIB electrolytes. The combination of the multiplexing technique and GCMS allows the analysis of fast decomposition processes by 15 fold increase of time resolution compared to conventional gas chromatography. In addition, FTIR allows online monitoring of selected vibration bands. Commercially produced pouch cells were monitored with respect to evolving gas species during battery operation under overcharge conditions. For the decomposition of LiPF6 / organic carbonate- based electrolytes alkanes, alcohols, ethers, esters, aldehydes and also derivatives that appear in the presence of hydrofluoric acid such as fluorinated alkane species, have been evaluated. The author gratefully acknowledges the FFG (Austrian Research Promotion Agency) for funding this research within project No. 858298.

A microwave assisted copper-catalyzed amination protocol is reported utilizing a series of 2,6-dihalo- and 2-amino-6-halo pyridine precursors. Using this procedure, selective substitution of one or two halogens by aryl or alkylamines was achieved within 2–6 h with temperatures between 80 and 225 °C affording 2,6-diaminopyridines in good to excellent isolated yields. The reaction allows easy variation between educts and different N -substitutions. The target compounds are valuable precursors for the synthesis of bis-phosphorylated 2,6-diaminopyridines which are used as PNP pincer ligands in transition metal complexes.

An amine based CO2 corrosion inhibitor and an imidazoline based CO2 corrosion inhibitor have been tested in a two-phase laboratory flow loop system under conditions of a gas condensate well in Austria. After a detailed description of the experimental setups, degradation rates of material API L-80 (UNS G41300) as function of flow velocity and inhibitor dosage are presented. Further, the influence of chloride addition on inhibitor performance has been investigated. All results are discussed with respect to critical inhibitor concentration to reach nearly 100 % inhibitor efficiency. Inhibitor A exhibits alkylamine as an active ingredient dissolved in ethylene glycol and different alcohols, and the effect of inhibitor B is based on imidazoline dissolved in different alcohols. Results demonstrate that the test rig delivers reasonable results with respect to inhibitor protection rates. Independent of superficial flow velocities (tested between 3 and 35 m/s), both inhibitors exhibit a good performance as long as dosed above their critical concentration. The critical concentration is clearly below 100 ppm to the liquid phase. The addition of chlorides affects the performance of the alkylamine based inhibitor significantly more than in case of the imidazoline.

A fast gas chromatography/mass spectrometry method was developed and validated for the analysis of the potential endocrine disrupters octinoxate and oxybenzone in swimming pool water samples based on the solvent-free solid-phase microextraction technique. The low-pressure gas chromatography/mass spectrometry method used for the fast identification of UV filter substances was compared to a conventional method in terms of sensitivity and speed. The fast method proposed resulted in 2 min runs, leading to an eightfold decrease in the total analysis time and a sevenfold improvement in detection limits. The main parameters affecting the solid-phase microextraction process were also studied in detail and the optimized conditions were as follows: fiber coating, polyacrylate; extraction mode, direct immersion; extraction temperature, 25°C; sample volume, 5 mL; extraction time 45 min; pH 6.5. Under the optimized conditions, a linear response was obtained in the concentration range of 0.5-25 μg/L with correlation coefficients in the range 0.990-0.999. The limits of detection were 0.17-0.29 μg/L, and the recoveries were 80-83%. Combined method uncertainty was assessed and found to be less than 7% for both analytes for concentrations equal to or higher than 5 μg/L. Pool water samples were analyzed to demonstrate the applicability of the proposed method. Neither octinoxate nor oxybenzone were detected in the swimming pool water samples at concentrations above the respective limits of detection.

Metal–organic frameworks (MOFs) are crystalline porous materials composed of metal ions or clusters coordinated with organic linkers. Due to their extraordinary properties such as high porosity with homogeneous and tunable in size pores/cages, as well as high thermal and chemical stability, MOFs have gained attention in diverse analytical applications. MOFs have been coupled with a wide variety of extraction techniques including solid-phase extraction (SPE), dispersive solid-phase extraction (d-SPE), and magnetic solid-phase extraction (MSPE) for the extraction and preconcentration of metal ions from complex matrices. The low concentration levels of metal ions in real samples including food samples, environmental samples, and biological samples, as well as the increased number of potentially interfering ions, make the determination of trace levels of metal ions still challenging. A wide variety of MOF materials have been employed for the extraction of metals from sample matrices prior to their determination with spectrometric techniques.

RATIONALE The capabilities of modified non-spherical Doehlert-type experimental designs to optimize the performance of a hybrid mass spectrometer were investigated in this paper for the first time. The optimization process was completed in three successive steps with groups of variables avoiding any univariable approach. Glutathione (GSH, reduced) was selected as a very interesting analyte since it is considered to be one of the most abundant tripeptides in human organism and its action against xenobiotics and oxidative radicals is well known. METHODS In particular, a tandem technique based on sequential ion management by an ion trap followed by a time-of-flight mass analyzer (ITTOFMS) was introduced commercially in recent years and investigated for glutathione determination. Glutathione was injected in a stream of a typical mobile phase used in liquid chromatography (LC) and analyzed after electrospray ionization (ESI) in tandem MS. RESULTS The three main steps of the LC/MS system, namely the LC mobile phase, the ESI interface and the MS analyzer, were independently optimized in terms of maximum sensitivity. In this context quadratic models were found and their prediction power was evaluated. A calibration study was performed at default and optimum conditions in order to quantitatively estimate the sensitivity enhancement of the employed technique for this analyte. Satisfactory precision (RSD 5.7%) and detectability (LOD 0.07 µmol L–1) were achieved. CONCLUSIONS The results highlighted the possibilities offered by the employment of multifactorial optimization towards the improvement of performance of tandem mass spectrometry techniques. Copyright © 2012 John Wiley & Sons, Ltd.

The simultaneous determination of selenomethionine, selenoethionine, selenocystine, dimethyldiselenide, and diphenyldiselenide was investigated for the first time by a hyphenated HPLC-IT-TOF-MS technique using atmospheric pressure chemical ionization (APCI). Alkylselenides and phenyldiselenides and also the most common selenoamino acids were successfully determined after optimization of the instrumental and procedural parameters of the above system. Non-polar columns were studied in order to obtain baseline separation and speciation in less than 10 min. Selenium speciation was achieved successfully after optimization of the instrumental and procedural parameters of the aforementioned system. The APCI interface was studied at different zone temperatures and the most characteristic ions for each analyte were defined using both positive and negative polarity. The detection limits of the six selenium species ranged between 13 and 59 µg/L and the relative standard deviation was between 4.2 and 9.3%, respectively.

The archaeological discoveries of Tang tomb murals in Xi’an, China brought to light unprecedented data for the study of the art of the Tang Dynasty (618-907 AD). The spectacular murals with their particular contents provided first-hand material for the study of Chinese history and the techniques of wall paintings during the Tang Dynasty. In order to gain a better understanding of the materials used and to preserve those paintings, pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) and gas chromatography-mass spectrometry (GC/MS) were applied for the characterization of the binding media in the paintings. The combination of these analytical techniques is an ideal methodology to identify binding media in unknown samples.

The Cretan School of iconography is the last great flowering of the traditional Byzantine painting manner, which is however influenced by different schools and western art. Despite their historical significance, icons of the Cretan School have been rarely studied through modern chemical techniques and therefore very few information is available on the materials used by the Cretan painters. In the present investigation, the organic materials contained in several icons of the Cretan School of Iconography from the collection of the Benaki Museum, Athens, Greece, are analyzed and identified by High Performance Liquid Chromatography coupled to a Diode Array Detector (HPLC–DAD) and Gas Chromatography with Mass Spectrometry (GC–MS). The HPLC–DAD results provide support to a recently published report which showed that kermes used in “Cretan” icons of 15th century and early 16th century was replaced by cochineal which was used in icons dated after early 16th century. This trend is known for western art and it is now proved for Cretan icons, showing thus the influence of the Cretan painters by other European painting schools. Other dyes detected in the historical samples, extracted from Cretan icons are madder (possibly Rubia tinctorum L., according to HPLC profiles) and indigoid dyes. Oils, such as linseed and walnut oil, are identified in samples extracted from the seven icons tested by GC–MS. Egg yolk is identified in the extract of only one icon and animal glue, originated most likely from the gesso ground, is found in six samples. Other organic materials detected by GC–MS were wax, as well as synthetic resins, applied during conservation treatments.

In accordance with Article 8 of the European Union (EU) Water Framework Directive (WFD), EU Member States are required to establish monitoring programs for the quality of the surface water and the groundwater within each river-basin district. As such data are the basis for regulatory decisions and measures required to achieve WFD environmental objectives, appropriate analytical quality-assurance and quality-control tools have to be implemented by the monitoring laboratories. In this respect, reference materials (RMs) play a key role. Within the framework of the SWIFT-WFD project (Screening methods for Water data InFormation in support of the WFD), several approaches to the preparation of matrix RMs for the analysis of polycyclic aromatic hydrocarbons and pesticides in water have been used in wide-scale proficiency-testing (PT) schemes. We present the different strategies employed in preparing water-matrix RMs for organic analytes. By reviewing the results from the SWIFT-WFD PT schemes, we reflect on the applicability and the suitability of the different approaches.